US4863994A - Use of monohydric alcohols in molded polyurethane resins - Google Patents

Use of monohydric alcohols in molded polyurethane resins Download PDF

Info

Publication number
US4863994A
US4863994A US07/210,958 US21095888A US4863994A US 4863994 A US4863994 A US 4863994A US 21095888 A US21095888 A US 21095888A US 4863994 A US4863994 A US 4863994A
Authority
US
United States
Prior art keywords
weight
percent
molded
equivalent weight
polyol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US07/210,958
Inventor
Donald L. Nelson
Douglas P. Waszeciak
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority to US07/210,958 priority Critical patent/US4863994A/en
Priority claimed from KR9070400A external-priority patent/KR930003710B1/en
Assigned to DOW CHEMICAL COMPANY, THE reassignment DOW CHEMICAL COMPANY, THE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: NELSON, DONALD L., WASZECIAK, DOUGLAS P.
Application granted granted Critical
Publication of US4863994A publication Critical patent/US4863994A/en
Anticipated expiration legal-status Critical
Application status is Expired - Lifetime legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805Compounds having only one group containing active hydrogen
    • C08G18/2815Monohydroxy compounds
    • C08G18/283Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805Compounds having only one group containing active hydrogen
    • C08G18/2815Monohydroxy compounds
    • C08G18/282Alkanols, cycloalkanols or arylalkanols including terpenealcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
    • C08G18/6517Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203 having at least three hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6523Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
    • C08G18/6535Compounds of group C08G18/3271
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2105/00Oligomerisation
    • C08G2105/02Oligomerisation to isocyanurate groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2120/00Compositions for reaction injection moulding processes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2130/00Compositions of compatibilising agents used in mixtures of high-molecular-weight compounds having active hydrogen with other compounds having active hydrogen
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31551Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31598Next to silicon-containing [silicone, cement, etc.] layer
    • Y10T428/31601Quartz or glass

Abstract

Disclosed are novel active hydrogen compositions comprising: (1) a polymeric polyol; (2) a low equivalent weight cross-linking polyol; (3) optionally a second polyol having an equivalent weight up to about 500; and (4) a sufficient amount of a monohydric alcohol of equivalent weight up to about 1,500 to provide a monophase low viscosity blend.
Also disclosed are the molded polyurethanes produced from the above compositions, and, particularly high strength mat molded reaction injection molded parts.

Description

FIELD OF THE INVENTION

This invention relates to molded polyurethanes and is more particularly concerned with mat-molded RIM (reaction injection molded) parts and active hydrogen compositions as precursors therefor.

DESCRIPTION OF THE PRIOR ART

The use of polyurethanes and/or polyisocyanurate resins in the preparation of molded articles used in a wide variety of applications is a well known field of technology. Further, the production of reinforced and mat-molded parts by the reaction injection molding procedure is also well known. For typical disclosures in such areas see U.S. Pat. Nos. 4,272,618; 4,296,212; 4,374,210; 4,433,067; 4,435,349; 4,530,941; and 4,546,114.

One of the difficulties in this field of technology is the fact that the so-called B side components required to react with the polyisocyanates invariably contain a number of ingredients which tend to be incompatible with each other, at least over an extended period of time. This is particularly true in the case of polymeric polyols mixed with lower molecular weight polyols such as glycols. Accordingly, there is a continual need for improved miscible blends of polymeric polyols with other active hydrogen containing compounds.

SUMMARY OF THE INVENTION

The present invention in its broadest scope is directed to active hydrogen compositions comprising a polymeric polyol having at least two hydroxyl groups, a low equivalent weight cross-liking polyol, optionally additional polyols having an equivalent weight up to about 500, and a sufficient amount of a monohydric alcohol of equivalent weight up to about 1500 to provide a monophase low viscosity blend.

A particular class of the above blends comprises:

(1) from about 4 to about 6 percent by weight of a polymeric polyol of molecular weight from about 1,500 to about 12,000 and functionality from about 2 to about 8;

(2) from about 2 to about 80 percent by weight of a cross-linking polyol of equivalent weight less than about 120 and functionality from about 3 to about 6;

(3) from zero to about 80 percent by weight of a difunctional extender of equivalent weight from about 30 to about 300; and

(4) from about 1 to about 90 percent by weight of an alkyleneoxy or polyalkyleneoxy monohydric alcohol of equivalent weight from about 90 to about 1,500 wherein the total combined weights of (1), (2), (3), and (4) equals 100 percent.

The invention is also directed to molded polyurethane polymers prepared by the reaction of organic polyisocyanates with the active hydrogen compositions set forth above, optionally in the presence of a urethane and/or isocyanurate forming catalyst.

The term "cross-linking polyol" as used herein means a polyhydric chain extender having a functionality greater than two and hydroxyl equivalent weight less than about 120.

The term "monophase" means a single phase or miscible in reference to the multicomponent blends of the invention at the time of any subsequent agitation.

The term "low viscosity" means a viscosity measured at 25° C. of less than about 800 cps (preferably less than about 400 cps.

The term "molecular weight" means the number average molecular weight as determined by end-group analysis or other colligative property measurement.

The term "equivalent weight" of any reactive species means its molecular weight divided by its particular number of reactive groups.

Notably, the active hydrogen compositions in accordance with the present invention depart radically from the prior art by containing substantial weight proportions of monofunctional or monohydric alcohols. Monofunctinal reactants particularly in polyurethane formation have been considered detrimental to resulting polymer physical properties due to their chain ending activity. Generally speaking, their use is prohibited. Surprisingly, the molded polyurethanes in accordance. with the present invention produced from the novel blends, while showing some property losses, retain more than sufficient physical properties to allow their use. Moreover, molded reinforced composites in accordance with the present invention can be prepared with improved toughness in spite of the monofunctional component. This improved toughness is accomplished without having to resort to the prior art use of expensive purified difunctional isocyanate components.

One of the unexpected advantages to flow from the present invention is the miscibility of the polyol compositions, notwithstanding the presence of notoriously insoluble extenders. Just as unexpected is the discovery that the solvency and presumably cutting or wetting capacity of the monohydric components results in polyol blends having very low viscosities as defined above. This in turn leads to excellent wet-out by the resinous polyurethane forming ingredients of any fibrous reinforcing material employed during the preparation of molded composites. All of these attributes of the active hydrogen compositions facilitate the processing of the polyurethane resin forming ingredients during the molding operations. It is in the formation of high strength reaction injection molded (RIM) composites with fiberglass that the present glycol compositions excel both in regard to their processing advantages and for the physical properties of the resulting RIM parts.

The molded products are useful as structural members in automotive applications, such as doors, hoods, skirts, load floors, instrument panels, and the like; in the manufacture of appliances, furniture, building construction panels, sporting goods equipment such as shin guards, chest protectors, and the like.

DETAILED DESCRIPTION OF THE INVENTION

The active hydrogen compositions defined above are readily prepared using any conventional means known to one skilled in the art for mixing liquid components together. This includes mixing the components manually or mechanically in small scale hand-mix procedures in suitable containers such as beakers, flasks, pails, and the like, up to large scale batch or continuous mixing in stirred kettles, vats, tanks, and the like. It is preferable, particularly if the compositions are not to be used immediately, or, are being manufactured on a large scale for packaging and eventual shipment and storage, that the components are mixed under the exclusion of air and atmospheric moisture. This is most readily accomplished by mixing under a positive pressure of an inert gas such as nitrogen, argon, and the like. Heating may or may not be necessary to effect the formation of the blends. If it is found expedient to do so for whatever reason such as when a low melting solid or waxy reactive hydrogen component is employed, then the components may be heated together at the necessary temperature to effect solution.

All of the components individually are well known to those skilled in this art, including the blending together of the polyhydric components. However, it is the addition of the monohydric alcohol component wherein the novelty resides. Accordingly, it is the latter component which is employed in sufficient proportions with respect to the others which gives rise to the monophase low viscosity blends as defined above.

The polymeric polyol component can be any organic polyol provided it has at least 2 hydroxyl groups and a molecular weight of at least 650. It is to be understood that, if desired, mixtures of polymeric polyols can be employed. Preferably, the polyol has a molecular weight from about 1,500 to about 12,000 with a functionality from about 2 to about 8 and includes polyether polyols, polyester polyols, reinforced or polymer polyols, polycarbonate polyols, resole polyols, polybutadiene based polyols, and the like. More preferably, the functionality is from about 2 to about 4 with the hydroxyl functionality being predominantly primary and a molecular weight from about 2,000 to about 6,000.

Illustrative, but not limiting, of the classes of polyols which can be used are the polyoxyalkylene polyethers; polyester polyols; polyol adducts derived from ethylene oxide with methylenedianiline and polymethylene polyphenylamine mixtures (in accordance with U.S. Pat. No. 3,499,009); polyols obtained by the Mannich condensation of a phenolic compound with formaldehyde, an alkanolamine, and ethylene oxide (in accordance with U. S. Pat. No. 3,297,597); vinyl reinforced polyether polyols, e.g. by the polymerization of styrene or acrylonitrile in the presence of the polyether; polyacetals prepared from glycols such as diethylene glycol and formaldehyde; polycarbonates, for example those derived from butanediol with diarylcarbonates; polyester amides; the resole polyols (see Prep. Methods of Polymer Chem. by W. R. Sorenson et al., 1961, page 293, Interscience Publishers, New York, N.Y.); and the polybutadiene resins having primary hydroxyl groups (see Poly Bd. Liquid Resins, Product Bulletin BD-3, October 1974, Arco Chemical Company, Div. of Atlantic Richfield, New York, N.Y.).

A preferred group of polyols comprises the polyalkyleneoxy polyols particularly the propyleneoxy-polyethyleneoxy capped diols, triols, and tetrols obtained by the alkoxylation of water, ammonia, ethylene glycol, propylene glycol, trimethylolpropane, aniline, ethanolamine, ethylene diamine, and the like; the polyester diols obtained from the reaction of dibasic carboxylic acids such as succinic, adipic, suberic, azelaic, phthalic, isophthalic, and the like with alkylene glycols and oxyalkylene glycols to form the corresponding polyalkylene, and polyoxyalkylene ester diols or copolymers thereof; polyester polyols derived from crude reaction residues and scrap polyester resin sources by their transesterfication with low molecular weight glycols; and the vinyl-resin reinforced propyleneoxy-ethyleneoxy capped diols and triols, particularly those polyethers reinforced with polyacrylonitrile.

Any cross-linking polyol or mixtures of such polyols meeting the definition set forth above can be employed. It will be readily apparent to one skilled in the art that such polyols must have functionalities greater than 2 and low equivalent weights so as not to dissipate the polyfunctionality simply in branching. It is preferable that its functionality fall within the range of from about 3 to about 6. More preferably the functionality is from about 3 to about 4 with a hydroxyl equivalent weight from about 50 to about 100. Illustrative but non-limiting thereof are ethylene oxide and/or propylene oxide and/or butylene oxide derivatives of such initiators as glycerine, trimethylolpropane, trimethylolethane, pentaerythritol, ethanolamine, diethanolamine, triethanolamine, ethylene diamine, propylene diamine, butylene diamine, diethylenetriamine, triethylenetetramine, inositol and derivatives thereof with ethylene and/or propylene oxide, and the like. The illustrative alkyleneoxy derivatives of the alkylene polyamines set forth above are found to be particularly advantageous in the compositions in accordance with the present invention.

The optional component has been defined above as additional polyols of equivalent weight up to about 500. While such a definition will include low molecular weight polyols overlapping with those polymeric polyols discussed above at the lower end of their range, a preferred group of optional components comprises the well known difunctional extenders having an equivalent weight range of from about 30 to about 300, and, preferably from about 30 to about 200.

Illustrative of such extenders are aliphatic straight and branched chain diols having from about 2 to 10 carbon atoms, inclusive, in the chain. Illustrative of such diols are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, 1,3-pentanediol, 1,2-hexanediol, 3-methylpentane-1,5-diol, 1,9-nonanediol, 2-methyloctane-1,8-diol, 1,4-cyclohexanedimethanol, hydroquinone bis(hydroxyethyl)ether, and the like including mixtures of two or more such diols. The extenders, which can be used alone or in admixture with each other or any of the above diols, also include diethylene glycol, dipropylene glycol, tripropylene glycol, and the like, as well as ester diols obtained by esterifying adipic, azelaic, glutaric and like aliphatic dicarboxylic acids with aliphatic diols such as those exemplified above utilizing from about 0.01 to about 0.8 mole of acid per mole of diol. Also included in the extenders which can be used in preparing the polyurethanes of the invention are the adducts obtained by reacting an aliphatic diol such as 1,4-cyclohexanedimethanol, neopentyl glycol, hexane-1,2-diol, ethylene glycol, butane-1,4-diol, and the like with ε-caprolactone in a mole ratio of from 0.01 to 2 moles of caprolactone per mole of diol or triol. Trifunctional extenders such as glycerol, trimethylolpropane and the like can also be employed in a minor proportion (less than 20 equivalent percent) with one or more of the above diols.

While any of the diol extenders described and exemplified above can be employed alone, or in admixture, it is preferred to use 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, either alone or in admixture with each other or with one or more aliphatic diols previously named.

The monohydric alcohol component as defined above has an equivalent weight of up to about 1,500. Since it is monofunctional, this means the equivalent weight is synonymous with molecular weight. Although not wishing the present invention to be limited by any theoretical considerations but only by the claims appended hereinbelow, it is believed that this component acts in the capacity of a wetting agent or surfactant. In this role it solubilizes the various components in the blend. Any monohydric alcohol or mixture of such alcohols falling within this definition may be employed in the present blends, although generally speaking their efficacy in solubilizing all the blend components and to lower blend viscosity will increase with increasing linear molecular conformation. Put in simpler terms, the longer the molecular distance between the hydroxyl function and the end of the molecule, the more efficient is the component in achieving its unexpected results in the compositions. However, there is a reasonable upper limit on this length which is best defined by the upper equivalent weight limit. In this same connection, it is preferred that it have a minimum equivalent weight of about 90. Advantageously, the equivalent weight will fall within a range of from about 90 to about 1,500, preferably, from about 200 to about 1,000 and, most preferably, from about 400 to about 600.

Illustrative but non-limiting of the monohydric alcohols are the C6 to C20 aliphatic alcohols such as hexanol, heptanol, octanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, and the like; although higher aliphatic alcohols may be used, the above range of alcohols are readily available commercially; the cellosolves and carbitols such as butyl cellosolve (monobutyl ether of ethylene glycol), carbitol (monoethyl ether of diethylene glycol), methyl carbitol (monomethyl ether of diethylene glycol), butyl carbitol (monobutyl ether of diethylene glycol), and the like; the ethylene oxide and/or propylene oxide and/or butylene oxide adducts of the well known alkylphenols such as butylphenol, pentylphenol, heptylphenol, octylphenol, nonylphenol, decylphenol, and the like; the polyalkyleneoxy adducts of lower aliphatic, cycloaliphatic, or aryl alcohols having the generic formula B(OCH2 CHR)x OH wherein B represents C1 to C8 alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and isomeric forms thereof; or C6 to C18 aryl such as phenyl, tolyl, naphthyl, and the like, or C5 to C7 cycloalkyl such as cyclopentyl, cyclohexyl, cycloheptyl; R represents hydrogen, methyl, or ethyl, or mixtures thereof in the same molecule, and x can have an average value from about 1 to about 30; the preferred limitations on this class of polyalkyleneoxy adducts are those wherein B is lower alkyl C1 to C4, R is hydrogen and/or methyl, and x has an average value from about 4 to about 15.

Of the various classes set forth above those falling within the alkyleneoxy or polyalkyleneoxy class are preferred because they offer the best overall properties both in regard to their efficacy in the compositions of the invention and because they are liquids at room temperature (circa 20° C.) as opposed to the long chain aliphatic alcohols, for example which are waxes or solids at room temperature therefore requiring the heating of the compositions during mixing. More preferred are the polyalkyleneoxy adducts of the lower aliphatic alcohols having a molecular weight of from about 200 to about 1,000, particularly those meeting the generic formula set forth above. Most preferred are those polyalkyleneoxy compounds which are polyethyleneoxy-capped polypropyleneoxy monohydric alcohols.

In respect of the proportions in which the various blend components can be employed together, it should be noted that a wide variation can be tolerated. Regardless of the proportions of the (1) polymeric polyol, (2) cross-linking polyol, and (3) optional polyol, sufficient proportions of (4) the monohydric alcohol must be present to compatibilize the other components together particularly the (2) and (3) components with the polymeric polyol at the time of any subsequent agitation. At the same time this minimum proportion of (4) should result in a lowering of the blend viscosity to the levels set forth above. It should be recognized that such blends of active hydrogen containing compositions can find a broad range of utilities which will dictate the desired proportions of each specific ingredient whether in polyurethane adhesive formulations, epoxy formulations, and the like. Such desired proportions are easily determined by simple trial and error experiments for each specific application. However, in respect of their utility in polyurethane formation, particularly molded polyurethane applications, there are optimum component proportions which are found to be most efficacious. In this connection, the expressed preferences set forth above for the individual components are made with a particular view to the preparation of molded polyurethane polymers. To this end, a particular class of active hydrogen compositions setting forth the identity and proportions of each of the components is described above. A preferred composition is as follows: (1) from about 7 to about 50 percent by weight of a polyalkyleneoxy polyol of molecular weight from about 2,000 to about 6,000 and functionality from about 2 to about 4, (2) from about 7 to about 70 percent by weight of a cross-linking polyol of equivalent weight from about 50 to about 100 and functionality from about 3 to about 4, (3) from zero to about 60 percent by weight of a difunctional extender of equivalent weight from about 30 to about 200, and (4) from about 4 to about 80 percent by weight of a polyalkyleneoxy monohydric alcohol of equivalent weight from about 200 to about 1,000 based on the combined component weights of 100 percent. An even more preferred range of proportions are from about 15 to about 35 percent of (1); from about 15 to about 50 percent of (2); from about 5 to about 30 percent of (3); and from about 10 to about 60 percent of (4).

The molded polyurethane polymers in accordance with the present invention can be prepard during any of the manual or machine mixing techniques known to this art. The molding operation can also be any of the known molding operations such as open or closed molds, casting the reactants into open molds which are then closed with vice clamps, pneumatically, or mechanically operated molds automatically opened and closed on a continuous turntable operation, and the like. A particularly facile method is the RIM procedure operated either in a static or continuous mode using the procedures for automatically opening/closing the molds, etc. Particular reference to RIM techniques can be found in U.S. Pat. Nos. 4,272,618; 4,296,212; 4,374,210; 4,433,067; 4,435,349; and 4,546,114 which patent disclosures relative thereto are incorporated herein by reference.

Any of the organic polyisocyanates employed in the art for the preparation of molded polyurethanes can be used herein. Included are those organic polyisocyanates disclosed in the incorporated references such as organic di- or higher functionality aliphatic or aromatic polyisocyanates. The preferred class comprises the aromatic polyisocyanates.

Illustrative, but not limiting thereof, are 1,6-hexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), m- and p-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate and mixtures of these two isomers, methylenebis(phenyl isocyanate) inclusive of 4,4'-methylenebis(phenyl isocyanate), 2,4'-methylenebis(phenyl isocyanate), and mixtures of these methylenebis(phenyl isocyanate) isomers, 3,3'-dimethyl-4,4'-diisocyanatodiphenyl methane; liquefied forms of methylenebis(phenyl isocyanate) particularly liquefied forms (including mixtures containing up to about 50 percent of the 2,4'-isomer) of 4,4'-methylenebis(phenyl isocyanate) such as the carbodiimide-containing 4,4'-methylenebis(phenyl isocyanates) having isocyanate equivalent weights of from about 130 to about 180 prepared for example by heating 4,4'-methylenebis(phenyl isocyanate) with a carbodiimide catalyst to convert a portion of said isocyanate to carbodiimide; and liquefied forms of 4,4'-methylenebis(phenyl isocyanate) which have been reacted with minor amounts (from about 0.04 to about 0.2 equivalent per equivalent of isocyanate) of low molecular weight glycols such as dipropylene glycol, tripropylene glycol, and mixtures thereof; isocyanate terminated prepolymers having an isocyanate content of about 9 to about 20 percent by weight prepared from methylenebis(phenyl isocyanate) and a polyol having a functionality from 2 to 3 selected from polyalkyleneoxy polyols of molecular weight 1000 to 10,000 polytetramethylene glycols of molecular weight 600 to 5000, and polyester polyols of molecular weight 500 to 8000, said polyol and said methylenebis(phenyl isocyanate) being reacted in the proportions of about 0.01 equivalent to about 0.5 equivalent of said polyol per isocyanate equivalent; blends or mixtures of the liquefied methylenebis(phenyl isocyanates) with each other and with the isocyanate terminated prepolymers described above in any proportions desired; polymethylene poly(phenyl isocyanate) mixtures containing from about 20 percent to about 85 percent by weight (preferably about 30 to about 60 percent) of methylenebis(phenyl isocyanate), with the balance of 80 to 15 percent by weight (70 to 40 percent) of the mixtures being polymethylene poly(phenyl isocyanates) of functionality higher than 2; included in the polymethylene poly(phenyl isocyanates) are those having the 4,4'-methylenebis(phenyl isocyanate) isomer and mixtures including up to about 30 percent of the corresponding 2,4'-isomer. One of the inherent advantages in the present polymers is the fact that they can be obtained with excellent physical properties while using the commercially attractive so-called crude polyisocyanate mixtures. To this extent, particularly preferred are the polymethylene poly(phenyl isocyanate) mixtures described above.

In its broadest scope the present invention comprehends the reaction of any one of the isocyanates described above or mixtures thereof with the active hydrogen compositions described in detail above. During the preparation of the polymers the components (1), (2), (3), and (4) need not be added as the premixed blend but can be added in any sequence or combination desired. In another embodiment, one or more of the components, particularly the polymeric polyol or optional polyol can be prereacted with polyisocyanate to form a soft or hard segment quasi-prepolymer or prepolymer which is then reacted with (2) and (4). In the most preferred and convenient embodiment, the ingredients are added as the premixed compositions described above in a one-spot process.

Accordingly, all of the subject matter and discussion set forth above in respect of the active hydrogen compositions along with the proportions including the preferred and more preferred limitations, apply with equal force in the preparation of the molded polyurethanes.

In its broadest scope the molded polyurethanes can be prepared optionally in the presence of a urethane and/or isocyanurate forming catalyst. The presence of the latter is dictated by the isocyanate to active hydrogen equivalents ratio. That is to say, if it is desired to have polyisocyanurate linkages along with the polyurethane in the resulting polymer, then a ratio exceeding about 1.15:1 is called for in conjunction with an isocyanurate forming catalyst. If mainly polyurethane linkages are desired and the active hydrogen containing components, particularly the cross-linker (2) contains a nitrogen atom which is autocatalytic in terms of urethane formation, then a urethane catalyst may not be necessary. Accordingly, the proportions of reactants are chosen such that the ratio of isocyanate equivalents to the total active hydrogen equivalents from (1), (2), (3), and (4) falls within a range of from about 0.85:1 to about 4:1 provided that when said ratio exceeds about 1.15:1 an isocyanurate catalyst is employed. Preferably, a urethane catalyst is employed with an isocyanate to total active hydrogen equivalent ratio falling within a range of from about 0.90:1 to about 1.15:1, and, most preferably 0.95:1 to 1.10:1.

Any of the urethane catalysts known in the art can be employed in catalytic amounts in the present process. Such catalysts include organic and inorganic acid salts of, and organometallic derivatives of bismuth, tin, lead, antimony, cobalt, and the like, as well as phosphines and tertiary organic amines. A preferred group of such catalysts include stannous octoate, stannous oleate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin mercaptopropionate, dibutyltin didodecylmercaptide, dibutyltin bis(isooctylthioglycolate), and the like; triethylamine, triethylenediamine, N,N,N',N'-tetramethylethylenediamine, N-methylmorpholine, N,N-dimethylcyclohexylamine, and the like, and mixtures of the above in any combination.

The trimerization catalyst if employed can be any catalyst known to those skilled in the art which will catalyze the trimerization of an organic isocyanate compound to form the isocyanurate moiety. For typical isocyanate trimerization catalysts see The Journal of Cellular Plastics, November/December 1975, page 329; and the patents cited supra which disclosures are already herein incorporated.

Typical catalyst classes are the glycine salts and tertiary amine trimerization catalysts and alkali metal carboxylic acid salts disclosed in the above patents and mixtures of the various types of catalysts. Some preferred species within the classes are sodium N-(2-hydroxy-5-nonylphenyl)methyl-N-methylglycinate, and N,N-dimethylcyclohexylamine, and mixtures thereof. Also included in the preferred catalyst components are the epoxides disclosed in U.S. Pat. No. 3,745,133.

The total quantity of catalyst if used, including mixtures thereof, can fall within a range of from about 0.001 percent by weight to about 5 percent based on total polyurethane or polyisocyanurate forming ingredients weight.

In an optional embodiment the polyurethane resin employed can be filled or reinforced in order to provide so-called RRIM articles. The fillers can be any of the conventional materials used in the art. Typically, these include flaked or milled glass, glass fibers in lengths of from about 1/16 inch to 1/4 inch, glass strands, and the like, alumina, titanium dioxide, calcium carbonate, talc, carbon black, powdered gypsum, natural clays such as kaolin, china clay, chopped rubber scrap, natural silica, and the like.

The fillers can be used in proportions of from about 1 to about 50 percent by weight based on the polyurethane resin forming ingredients, and, preferably, from about 5 to about 30 percent by weight.

Other optional additives can be employed in the resin forming ingredients. Typical of such additional components are wax lubricants, antioxidants, internal mold release agents, flame retardants, colorants, and the like. Typical but non-limiting flame retardant additives are the phosphorus containing flame retardants including those having active hydrogen reactivity (hydroxyl and amine groups) such as dibromoeopentyl glycol, tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate, tris(2,3-dibromopropyl)phosphate, tri(1,3-dichloroisopropyl)phosphate, and the like.

It is in the preparation of high strength molded composites wherein the present active hydrogen compositions and the resulting polyurethanes excel. The term "high strength" means having a flex modulus of at least 200,000 psi and preferably from about 200,000 to 5,000,000 psi. The term "composite" as it refers to the products made in accordance with the present invention has the significance generally accepted in the molding art to include the use of fibrous matted material embedded into, or impregnated by, the resin component which in the present case is preferably a polyurethane resin. The term does not include loose fibrous material. The term includes in its scope mat molded RIM (or MMRIM) articles. Additionally, included in the present process are the use of the fillers set forth above.

The term "fibrous material" does mean a fibrous material in the form of a mat. The fibrous components can be held within the mat form by mechanical forces but more often by the use of a polymeric adhesive such as a polyvinyl acetate, polyester, polyepoxide, and the like, or else by being woven or stitched. The fibrous arrangement in the mat can be random or oriented, and the like. Illustratively the fibrous material can be glass fiber, or an organic fiber inclusive of graphite fiber, polyester fiber, polyamide fiber, polyaramid fiber, and the like. The above fibrous materials are meant to be extremely only with the present process not limited solely to these examples. Any fibrous mat material can be employed in the present method. Although glass fibrous material is most preferred in the weight proportions set forth below.

At least one mat is employed in the process of the invention and preferably a plurality thereof with the only limitation in numbers being imposed by practical considerations and by the thickness of the molded part being prepared and the thickness of the mats involved. It is also advantageous to employ combinations of at least one organic fiber mat along with the at least one fiberglass mat.

The mats are placed in the mold either manually or by a mechanical delivery system prior to placing the mold cover in position.

The weight percent contributed to the composite will vary considerably depending on the type of fibrous material employed. Advantageously, it will fall within the range of from about 10 to about 70 weight percent, preferably from about 10 to about 60 weight percent.

Although it is not an essential requirement in the process of the present invention, it is preferred that the molds be at a temperature above ambient room temperatures when they receive the resin forming ingredients. Advantageously, the mold temperatures fall within the range of from about 120° F. to about 220° F. It will be readily understood that mold temperatures will vary depending on whether polyurethane or polyurethane-polyisocyanurate is being prepared; for the former, mold temperatures of about 120° F. to about 170° F. are advantageous while a range of from about 160° F. to about 220° F. is more useful for the latter.

The RIM molded composites in accordance with the invention in spite of a high weight percentage content of monofunctional ingredients have perfectly adequate physical properties to allow their utility in the end-use applications set forth above. In fact, in some instances the improvement observed in modulus, impact strengths, and toughness more than make up for whatever losses may be noted in other less important properties. This increased toughness also aids in part demolding as the flash tends to stay with the part instead of adhering to the mold. Also, as noted above, the facility with which the fiberglass mats can be wetted out to result in low void contents and very smooth surfaces of the molded parts attests to the value of the active hydrogen compositions of the invention because of the addition of the monohydric component.

The following examples describe the manner and process of making and using the invention and set forth the best mode contemplated by the inventors of carrying out the invention but are not to be construed as limiting.

EXAMPLE 1

This experiment describes the preparation of three active hydrogen compositions and their employment in preparing molded polyurethanes (runs 1 to 3) all in accordance with the present invention and the preparation of a comparison blend and molded polyurethane not so in accordance.

The components of the four blends are mixed together in the properties of parts by weight set forth in Table I. As noted below, the viscosities of the initially mixed blends are measured before any other ingredients are added and the same blends visually observed after standing for 24 hours for any evidence of separation. The comparison blend with no monohydric alcohol settles into two layers or two phases in less than 24 hours and its viscosity prior to separation is measured as 998 cps (25° C.). Significantly, the blends 1 to 3 do not phase separate and their viscosities are dramatically lower as compared with the comparison blend. The cutting and solvency power of the monohydric alcohol component gives rise to the unexpected stability and lowered viscosities of the blends 1 to 3.

In the preparation of the molded polyurethanes, the A tank of a Krauss-Maffei Model PU-40 RIM machine is charged with the polyisocyanate component at about 85° F. component temperature. The B tank is charged with the active hydrogen composition ingredients in the proportions set forth in Table I along with a polyurethane catalyst. The catalyst level for runs 1 to 3 represents about 0.1 weight percent based on total polyol component. A lower catalyst percentage of 0.05 weight percent for the comparison run reflects the higher tertiary amine content in this control. The B temperature is adjusted to about 115° F. Metering pumps from each tank are used to deliver the A and B components in the proportions set forth in Table I at 1,000 psi into the impingement mixing head of the RIM machine. The isocyanate to active hydrogen ratio for all runs is 1.05. After mixing, the reaction mixture is directed into a center gated metal mold measuring 36 inches×16 inches×3/16 inch at 140° F.

While the presence of the monohydric alcohol tends to diminish modulus properties of unfilled resin system, particularly at higher levels, its negative effect is minimal and within quite acceptable levels. In fact, run 1 at a lower level of monohydric alcohol is characterized by some measurably superior physical properties over the comparison molding. Improved processability due to lower blend B viscosity and the stability of the latter offsets the drop-off in physical properties of resulting molded products.

              TABLE I______________________________________        Compar-Runs         ison        1       2     3______________________________________Ingredients(pts. by wt.):Component APolyisocyanate.sup.1        184         192     201   218Component BPolyol.sup.2 45          45      45    45Cross-linking polyol.sup.3        50          50      50    50Diethylene glycol        30          30      30    30Monohydric alcohol.sup.4        --          30      60    120Urethane catalyst.sup.5        0.06        0.15    0.18  .24Blend B Properties.sup.6Number of phases        2           1       1     1Viscosity cps    25° C.            998         298   284   200    50° C.            214         81    81    59PropertiesSpecific gravity        1.19        1.19    1.20  1.18Flex strength (psi)        10,000      10,600  8,000 4,500Flex modulus (psi)        255,000     266,000 199,000                                  96,300Tensile strength        7,220       6,780   5,360 3,050(psi)Tensile modulus (psi)        209,000     178,000 174,800                                  88,300% Elongation 14          18.9    22    28HDT @ 264 psi (°C.).sup.7        90          68      51    44Notched Izod.sup.8        1.4         1.0     1.0   0.8(ft.-lbs./in.)______________________________________ Footnotes to Table I .sup.1 Polyisocyanate: a polymethylene poly(phenyl isocyanate) mixture comprising a methylenebis(phenyl isocyanate) content of about 45 percent by weight and the remainder comprising polymethylene poly(phenyl isocyanate) of functionality greater than 2; I.E. = about 134. .sup.2 Polyol: A polyethyleneoxypolypropyleneoxy triol; molecular weight about 5,000. .sup.3 Cross-linker: A mixed ethylene/propyleneoxide adduct of ethylene diamine; eq. wt. = about 70; functionality = about 4. .sup.4 Monohydric alcohol: A butyl alcohol initiated polyethyleneoxypolypropyleneoxy monohydric alcohol; eq. wt. = about 500. .sup.5 Urethane catalyst: A dibutyltin dialcoholate polyurethane catalyst supplied by Witco Chemical Corporation under the trade name UL38. .sup.6 Blend B properties: The blends of polyol, crosslinking polyol, diethylene glycol and monohydric alcohol in the case of runs 1 to 3 are initially mixed and their viscosities measured at both 25° C. and 50° C.; after 24 hours the blends are observed visually for phase separation; no other ingredients are added to the test blends. .sup.7 HDT: Heat deflection temperature determined in accordance with AST Test Method D648. .sup.8 Notched Izod: Impact strength measured in accordance with ASTM Tes Method D25656.
EXAMPLE 2

This experiment describes the preparation of a series of molded high strength composites consisting of fiberglass mats impregnated with reaction injection molded polyurethane polymer.

The same procedure and formulations set forth above in Example 1 and Table I under the headings comparison and 1 to 3 are employed in this series except that fiberglass mats are additionally employed. The appropriate number of 2 oz./sq. ft. fiberglass mats are cut to size just to fill the mold and laid flat one on top of the other prior to closing the mold and shooting the RIM mixture therein.

In a first series, two of the fiberglass mats are used in each one of the moldings. In runs 1(a) to 3(a) in accordance with the present invention, the polyurethane formulations corresponding to runs 1 to 3 described above are used. The comparison (a) run corresponding to the polyurethane formulation used in the comparison run (Table I) without monohydric alcohol is used with two of the mats. Similarly, in a second series except for the use of four of the glass mats instead of two, there are prepared runs 1(b) to 3(b) and their comparison (b) with no monohydric alcohol. The physical properties for these molded parts are set forth in Table II below.

The blends of the invention because of their superior processability and low viscosity result in improved glass wet out as evidenced by lack of voids and excellent surface smoothness in the molded parts of runs 1(a) to 3(a) and 1(b) to 3(b). The comparison (a) and (b) parts contain voids and lack the same surface smoothness.

In examining the measured physical properties set forth in Table II there is no large decrease in properties at either the 25 nor 45 weight percent glass content over the comparison (a) and (b). In fact, overall toughness and modulus properties can be improved over the control while employing the monofunctional alcohol component.

                                  TABLE II__________________________________________________________________________      Compari-         Compari-Runs       son (a)           1(a)               2(a)                   3(a)                       son (b)                            1(b) 2(b) 3(b)__________________________________________________________________________Number of mats.sup.1      2    2   2   2   4    4    4    4Glass content      25   25  25  25  45   45   45   45(wt. %)PropertiesSpecific gravity      1.44 1.39               1.37                   1.40                       1.59 1.52 1.53 1.59Flex strength      26,700           26,000               20,500                   19,600                       37,700                            37,900                                 37,500                                      28,700(psi)Flex modulus (psi)      774,000           838,000               586,000                   595,000                       1,153,000                            1,220,000                                 1,238,000                                      1,029,000Tensile strength      20,300           17,000               15,700                   15,400                       27,200                            29,000                                 30,200                                      28,500(psi)Tensile modulus      875,800           829,000               727,000                   688,000                       1,182,000                            1,317,000                                 1,379,000                                      1,233,000(psi)% Elongation      3    3   3   3   3    3    3    3HDT @ 264 psi (°C.)      193.6           195 175 183 208  206  205  196Notched Izod      9    8   9   11  15   15   15   20(ft-lbs./in.)__________________________________________________________________________ Footnote to Table II .sup.1 Mats are 2 oz./sq. ft. continuous strand fiberglass mats bonded together by a polyester resin and supplied under the designation M8610 by Owens Corning Fiberglass.
EXAMPLE 3

This experiment describes the preparation of two RRIM samples 1(c) and 1(f) and four composites 1(d), 1(e), 1(g), and 1(h) all in accordance with the present invention.

The same procedure and formulation set forth above in Example 1, run 1 is employed for 1(c) and 1(f) except for the inclusions in the respective formulations of alumina trihydrate and calcium carbonate fillers in the proportions of parts by weight set forth in Table III below. Similarly, the same procedure and formulation set forth above in Example 2 under the 1(a) and 1(b) samples dealing with glass mats is employed in the 1(d, e, g, and h) runs except for the inclusions of fillers and the variations in the number of glass mats as noted in Table III. The glass mats are the same 2 oz./sq. ft. fiberglass mats described in Example 2. It will be noted that a common formulation is used in all these 1(c to h) samples which is based on the run 1 set forth in Table I of Example 1. Accordingly, it is the series of properties for this run 1 which can be directly compared with the properties set forth in Table III.

In the case of the filled samples 1(c) and 1(f), the alumina trihydrate results in overall property improvements over the run 1 above with the exception of elongation. Calcium carbonate in this particular formulation does not provide the same improvements as alumina trihydrate but still provides adequate properties as set forth in 1(f) in Table III. The composite samples 1(d), 1(e), 1(g), and 1(h) show the dramatic increase in modules, impact strengths, toughness, and heat resistance properties (HDT data) when compared with the properties of run 1 of Table I above.

                                  TABLE III__________________________________________________________________________Runs       1(c)          1(d)              1(e)                  1(f)                      1(g)                          1(h)__________________________________________________________________________Number of mats      --  1   1   --  1   2Glass content      --  15  15  --  15  25(wt. %)Alumina trihydrate      30  15  30  --  --  --pts. by wt.Calcium carbonate      --  --  --  15  15  15pts. by wt.PropertiesSpecific gravity      1.35          1.30              1.44                  1.21                      1.24                          1.32Flex strength (psi)      10,400          16,600              18,500                  7,290                      14,200                          21,800Flex modulus (psi)      393,000          507,000              684,000                  196,000                      414,000                          663,000Tensile strength (psi)      7,860          10,000              10,100                  4,660                      8,990                          14,600Tensile modulus (psi)      416,000          556,000              796,000                  184,000                      470,000                          797,000% Elongation      2.9 2.4 1.3 5.8 2.5 2.4HDT @ 264 psi (°C.)      69  107 96  56  88  168Notched Izod      0.5 5.5 5.2 0.5 4.6 7.7(ft.-lbs./in.)__________________________________________________________________________

Claims (26)

What is claimed is:
1. An active hydrogen composition comprising (1) from about 4 to about 60 percent by weight of a polymeric polyol having at least two hydroxyl groups, (2) from about 2 to about 80 percent by weight of a low equivalent weight cross-linking polyol having a functionality greater than two, (3) from zero to about 80 percent by weight of additional polyols having an equivalent weight up to about 500, and (4) from about 1 to about 90 percent by weight of a monohydric alcohol of equivalent weight up to about 1,500 to provide a monophase low viscosity blend.
2. A composition according to claim 1 wherein said components comprise: (1) from about 4 to about 60 percent by weight of a polymeric polyol of molecular weight from about 1,500 to about 12,000 and functionality from about 2 to about 8; (2) from about 2 to about 80 percent by weight of a cross-linking polyol of equivalent weight less than about 120 and functionality from about 3 to about 6; (3) from zero to about 80 percent by weight of a difunctional extender of equivalent weight from about 30 to about 300; and (4) from about 1 to about 90 percent by weight of an alkyleneoxy or polyalkyleneoxy monohydric alcohol of equivalent weight from about 90 to about 1,500.
3. A composition according to claim 2 comprising
(1) from about 7 to about 50 percent by weight of a polyalkyleneoxy polyol of molecular weight from about 2,000 to about 6,000 and functionality from about 2 to about 4;
(2) from about 7 to about 70 percent by weight of a cross-linking polyol of equivalent weight from about 50 to about 100 and functionality from about 3 to about 4;
(3) from zero to about 60 percent by weight of a difunctional extender of equivalent weight from about 30 to about 200; and
(4) from about 4 to about 80 percent by weight of a polyalkyleneoxy monohydric alcohol of equivalent weight from about 200 to about 1,000.
4. A composition according to claim 3 wherein said (1) comprises a polyethyleneoxy-polypropyleneoxy triol of molecular weight about 5,000.
5. A composition according to claim 4 wherein said (2) comprises an ethylene and/or propylene oxide derivative of ethylene diamine.
6. A composition according to claim 5 wherein said (3) comprises diethylene glycol.
7. A composition according to claim 6 wherein said (4) comprises a butyl alcohol initiated polyethyleneoxy-polypropyleneoxy monohydric alcohol of equivalent weight about 500.
8. A molded polyurethane polymer having a flex modulus of at least 200,000 psi prepared by the reaction of an organic polyisocyanate, an active hydrogen composition according to claim 1 and, optionally, a urethane and/or isocyanurate forming catalyst.
9. A molded polymer according to claim 8 wherein said polyisocyanate comprises polymethylene poly(phenyl isocyanate).
10. A molded polymer according to claim 8 wherein said polymeric polyol has a molecular weight from about 1,500 to about 12,000 and functionality of about 2 to about 8.
11. A molded polymer according to claim 8 wherein said cross-linking polyol has an equivalent weight of less than about 120 and functionality from about 3 to about 6.
12. A molded polymer according to claim 8 wherein said optional polyol comprises an extender of equivalent weight from about 30 to about 300 and functionality of about two.
13. A molded polymer according to claim 8 wherein said monohydric alcohol comprises an alkyleneoxy or polyalkyleneoxy monohydric alcohol of equivalent weight from about 90 to about 1,500.
14. A molded polymer according to claim 8 wherein the proportions of reactants are such that the ratio of isocyanate equivalents to the total active hydrogen equivalents fall within a range from about 0.85:1 to about 4:1 provided that when said ratio exceeds about 1.15:1 an isocyanurate catalyst is employed.
15. A molded polymer according to claim 8 additionally comprising a fibrous reinforcing material.
16. A molded polymer according to claim 15 wherein said reinforcing material comprises at least one fiberglass mat.
17. A molded polymer according to claim 16 comprising a plurality of fiberglass mats.
18. A molded polymer according to claim 16 wherein the fiberglass content is about 10 to about 70 percent by weight of said molded polymer.
19. A molded polymer according to claim 8 additionally comprising a filler.
20. A high strength molded composite having a flex modulus of at least 200,000 psi comprising at least one fiberglass mat impregnated with a reaction injection molded polyurethane polymer prepared by the reaction of:
(A) a polymethylene poly(phenyl isocyanate);
(B) an active hydrogen composition comprising:
(1) from about 4 to 60 percent by weight of a polymeric polyol of molecular weight from about 1,500 to about 12,000 and functionality from about 2 to about 8;
(2) from about 2 to about 80 percent by weight of a cross-linking polyol of equivalent weight less than about 120 and functionality from about 3 to about 6;
(3) from zero to about 80 percent by weight of a difunctional extender of equivalent weight from about 30 to about 300; and
(4) from about 1 to about 90 percent by weight of an alkyleneoxy or polyalkyleneoxy monohydric alcohol having an equivalent weight from about 90 to about 1,500; wherein the total combined weights of (1), (2), (3), and (4) equals 100 percent and
(C) a urethane catalyst, wherein the proportions of reactants are such that the ratio of isocyanate equivalents to total active hydrogen equivalents from (B) falls within a range of from about 0.90:1 to about 1.15:1.
21. A molded composite according to claim 20 wherein said active hydrogen composition (B) comprises
(1) from about 7 to about 50 percent by weight of a polyalkyleneoxy polyol of molecular weight from about 2,000 to about 6,000 and functionality from about 2 to about 4;
(2) from about 7 to about 70 percent by weight of a cross-linking polyol of equivalent weight from about 50 to about 100 and functionality from about 3 to about 4;
(3) from zero to about 60 percent by weight of a difunctional extender of equivalent weight from about 30 to about 200; and
(4) from about 80 percent by weight of a polyalkyleneoxy monohydric alcohol of equivalent weight from about 200 to about 1,000.
22. A molded composite according to claim 21 wherein said fiberglass content is from about 10 to about 60 percent by weight of said composite.
23. A molded composite according to claim 22 wherein said (B1) is a polyethyleneoxy-polypropyleneoxy triol of molecular weight about 5,000.
24. A molded composite according to claim 23 wherein said (B2) is an ethylene and/or propylene oxide derivative of ethylene diamine.
25. A molded composite according to claim 24 wherein (B3) is diethylene glycol.
26. A molded composite according to claim 25 wherein (B4) is butyl alcohol initiated polyethyleneoxy-polypropyleneoxy monohydric alcohol of equivalent weight of about 500.
US07/210,958 1988-06-24 1988-06-24 Use of monohydric alcohols in molded polyurethane resins Expired - Lifetime US4863994A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US07/210,958 US4863994A (en) 1988-06-24 1988-06-24 Use of monohydric alcohols in molded polyurethane resins

Applications Claiming Priority (11)

Application Number Priority Date Filing Date Title
US07/210,958 US4863994A (en) 1988-06-24 1988-06-24 Use of monohydric alcohols in molded polyurethane resins
CA 602262 CA1333437C (en) 1988-06-24 1989-06-09 Use of monohydric alcohols in molded polyurethane resins
DE1989623879 DE68923879T2 (en) 1988-06-24 1989-06-16 Use of monohydric alcohols in cast polyurethane plastics.
EP19890907599 EP0422080B1 (en) 1988-06-24 1989-06-16 The use of monohydric alcohols in molded polyurethane resins
AU38435/89A AU634480B2 (en) 1988-06-24 1989-06-16 The use of monohydric alcohols in molded polyurethane resins
DE1989623879 DE68923879D1 (en) 1988-06-24 1989-06-16 Use of monohydric alcohols in cast polyurethane plastics.
AT89907599T AT126525T (en) 1988-06-24 1989-06-16 Use of monohydric alcohols in cast polyurethane plastics.
PCT/US1989/002652 WO1989012654A1 (en) 1988-06-24 1989-06-16 The use of monohydric alcohols in molded polyurethane resins
BR8907502A BR8907502A (en) 1988-06-24 1989-06-16 The use of monohydric alcohols in polyurethane resins molded
JP50715289A JPH03505468A (en) 1988-06-24 1989-06-16
KR9070400A KR930003710B1 (en) 1988-06-24 1989-06-16 The use of monohydric alcohol in molded polyurethane resins

Publications (1)

Publication Number Publication Date
US4863994A true US4863994A (en) 1989-09-05

Family

ID=22785031

Family Applications (1)

Application Number Title Priority Date Filing Date
US07/210,958 Expired - Lifetime US4863994A (en) 1988-06-24 1988-06-24 Use of monohydric alcohols in molded polyurethane resins

Country Status (9)

Country Link
US (1) US4863994A (en)
EP (1) EP0422080B1 (en)
JP (1) JPH03505468A (en)
AT (1) AT126525T (en)
AU (1) AU634480B2 (en)
BR (1) BR8907502A (en)
CA (1) CA1333437C (en)
DE (2) DE68923879T2 (en)
WO (1) WO1989012654A1 (en)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0464464A1 (en) * 1990-06-28 1992-01-08 BASF Corporation Polyurethane-polyisocyanurate structural RIM systems with enhanced processing
EP0609840A1 (en) * 1993-02-02 1994-08-10 Nippon Paint Co., Ltd. Polyurea resin composition
DE4333106A1 (en) * 1993-09-29 1995-03-30 Bayer Ag Mixtures of relatively high-molecular-weight polyols, finely divided polyurethane powder and nonvolatile viscosity reducers, polyurethanes obtainable therefrom, and specific viscosity reducers
US5545706A (en) * 1995-05-09 1996-08-13 Arco Chemical Technology, L.P. PTMEG polyurethane elastomers employing monofunctional polyethers
US6420493B1 (en) 2000-05-29 2002-07-16 Resin Systems Inc. Two component chemically thermoset composite resin matrix for use in composite manufacturing processes
WO2002094902A1 (en) 2001-05-21 2002-11-28 Huntsman International Llc Very soft polyurethane elastomer
EP1273607A1 (en) * 2000-04-04 2003-01-08 Battelle Memorial Institute Polyurethane and elastic fiber obtained therefrom
US6545118B1 (en) * 2000-12-05 2003-04-08 The United States Of America As Represented By The Secretary Of The Navy Polymer having network structure
US20040115420A1 (en) * 2002-11-12 2004-06-17 Schoemann Michael P. Ultrathin structural panel with rigid insert
US20040194881A1 (en) * 2003-04-04 2004-10-07 Ju-Ming Hung Easy de-glazing reactive hot melt adhesive
US20060189782A1 (en) * 2005-02-18 2006-08-24 Peters David D Elastomeric material
US7112631B2 (en) 2002-10-24 2006-09-26 National Starch And Chemical Investment Holding Corporation Moisture cured reactive hot melt adhesive with monofunctional reactants as grafting agents
WO2007107210A1 (en) * 2006-03-20 2007-09-27 Henkel Ag & Co. Kgaa Soft crosslinkable polyurethane materials
US20100152381A1 (en) * 2008-12-12 2010-06-17 Savino Thomas G Prepolymer systems having reduced monomeric isocyanate contents
US7875675B2 (en) 2005-11-23 2011-01-25 Milgard Manufacturing Incorporated Resin for composite structures
US7901762B2 (en) 2005-11-23 2011-03-08 Milgard Manufacturing Incorporated Pultruded component
ITMI20100440A1 (en) * 2010-03-18 2011-09-19 Dow Global Technologies Inc Process for the preparation of polyurethanes reinforced with long fibers that contain particulate fillers
US8101107B2 (en) 2005-11-23 2012-01-24 Milgard Manufacturing Incorporated Method for producing pultruded components
WO2013072380A2 (en) 2011-11-16 2013-05-23 Soudal Improved polyurethane foam composition
US8597016B2 (en) 2005-11-23 2013-12-03 Milgard Manufacturing Incorporated System for producing pultruded components
US20160297918A1 (en) * 2013-12-09 2016-10-13 Dow Global Technologies Llc Improved polyurethane prepolymers having little or no plasticizer and their use in vehicular glass adhesives

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3189578A (en) * 1959-04-23 1965-06-15 Deering Milliken Res Corp Polymers and their production
US3875086A (en) * 1973-08-10 1975-04-01 Jefferson Chem Co Inc Urethane containing monohydric polyether chain stoppers
US4371476A (en) * 1978-12-26 1983-02-01 Basf Wyandotte Corporation Mold release agents containing oxidation stable polyoxyalkylenes
US4581386A (en) * 1985-05-23 1986-04-08 Mobay Chemical Corporation Internal mold release agent for use in reaction injection molding
US4615822A (en) * 1983-06-27 1986-10-07 Stepan Company Compatibilized polyester polyol blend from phthalic anhydride bottoms
US4727868A (en) * 1984-11-13 1988-03-01 Thermedics, Inc. Anisotropic wound dressing

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4098772A (en) * 1976-03-11 1978-07-04 The Upjohn Company Thermoplastic polyurethanes prepared with small amounts of monohydric alcohols
FR2396035A1 (en) * 1977-07-01 1979-01-26 Progil Bayer Ugine Polyurethane foam prepd. from poly:hydroxylated polyether - and small amt. of mono:hydroxy deriv. to improve mould release property of prod.
US4329442A (en) * 1981-02-13 1982-05-11 Minnesota Mining And Manufacturing Company High adhesion plugging and encapsulating polyurethane prepared from a polyol, a tri or tetra functional aliphatic polyol and a monofunctional aliphatic alcohol
DE3344693A1 (en) * 1983-12-10 1985-06-20 Bayer Ag Aqueous solutions or dispersions of polyisocyanate polyaddition products, a process for their preparation, and to their use as adhesives or for the preparation of
JPH04487B2 (en) * 1984-12-24 1992-01-07 Mitsui Toatsu Chemicals
US4673696A (en) * 1986-07-03 1987-06-16 Ashland Oil, Inc. Thermoset molding compositions
US4794147A (en) * 1987-07-24 1988-12-27 Basf Corporation, Inmont Division Novel non-ionic polyurethane resins having polyether backbones in water-dilutable basecoats
GB8809754D0 (en) * 1988-04-25 1988-06-02 Ici Plc Polyurethane foams

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3189578A (en) * 1959-04-23 1965-06-15 Deering Milliken Res Corp Polymers and their production
US3875086A (en) * 1973-08-10 1975-04-01 Jefferson Chem Co Inc Urethane containing monohydric polyether chain stoppers
US4371476A (en) * 1978-12-26 1983-02-01 Basf Wyandotte Corporation Mold release agents containing oxidation stable polyoxyalkylenes
US4615822A (en) * 1983-06-27 1986-10-07 Stepan Company Compatibilized polyester polyol blend from phthalic anhydride bottoms
US4727868A (en) * 1984-11-13 1988-03-01 Thermedics, Inc. Anisotropic wound dressing
US4581386A (en) * 1985-05-23 1986-04-08 Mobay Chemical Corporation Internal mold release agent for use in reaction injection molding

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0464464A1 (en) * 1990-06-28 1992-01-08 BASF Corporation Polyurethane-polyisocyanurate structural RIM systems with enhanced processing
EP0609840A1 (en) * 1993-02-02 1994-08-10 Nippon Paint Co., Ltd. Polyurea resin composition
DE4333106A1 (en) * 1993-09-29 1995-03-30 Bayer Ag Mixtures of relatively high-molecular-weight polyols, finely divided polyurethane powder and nonvolatile viscosity reducers, polyurethanes obtainable therefrom, and specific viscosity reducers
CN1089772C (en) * 1995-05-09 2002-08-28 阿科化学技术公司 Improved PTMEG polyurethane elastomers employing monofunctional polyesters
US5545706A (en) * 1995-05-09 1996-08-13 Arco Chemical Technology, L.P. PTMEG polyurethane elastomers employing monofunctional polyethers
AU694644B2 (en) * 1995-05-09 1998-07-23 Arco Chemical Technology L.P. Improved PTMEG polyurethane elastomers employing monofunctional polyethers
EP1273607A1 (en) * 2000-04-04 2003-01-08 Battelle Memorial Institute Polyurethane and elastic fiber obtained therefrom
EP1273607A4 (en) * 2000-04-04 2003-05-02 Battelle Memorial Institute Polyurethane and elastic fiber obtained therefrom
US6420493B1 (en) 2000-05-29 2002-07-16 Resin Systems Inc. Two component chemically thermoset composite resin matrix for use in composite manufacturing processes
US6545118B1 (en) * 2000-12-05 2003-04-08 The United States Of America As Represented By The Secretary Of The Navy Polymer having network structure
WO2002094902A1 (en) 2001-05-21 2002-11-28 Huntsman International Llc Very soft polyurethane elastomer
US20040138390A1 (en) * 2001-05-21 2004-07-15 Bleys Gerhard Jozef Elastomeric polyurethane material
AU2002257788B2 (en) * 2001-05-21 2007-09-20 Huntsman International Llc Very soft polyurethane elastomer
US6914117B2 (en) 2001-05-21 2005-07-05 Huntsman International Llc Elastomeric polyurethane material
CZ297662B6 (en) * 2001-05-21 2007-02-28 Huntsman International Llc Very soft polyurethane elastomer�
US7112631B2 (en) 2002-10-24 2006-09-26 National Starch And Chemical Investment Holding Corporation Moisture cured reactive hot melt adhesive with monofunctional reactants as grafting agents
US7066532B2 (en) 2002-11-12 2006-06-27 Lear Corporation Ultrathin structural panel with rigid insert
US20040115420A1 (en) * 2002-11-12 2004-06-17 Schoemann Michael P. Ultrathin structural panel with rigid insert
US20040194881A1 (en) * 2003-04-04 2004-10-07 Ju-Ming Hung Easy de-glazing reactive hot melt adhesive
US20060189782A1 (en) * 2005-02-18 2006-08-24 Peters David D Elastomeric material
US8101107B2 (en) 2005-11-23 2012-01-24 Milgard Manufacturing Incorporated Method for producing pultruded components
US7901762B2 (en) 2005-11-23 2011-03-08 Milgard Manufacturing Incorporated Pultruded component
US8597016B2 (en) 2005-11-23 2013-12-03 Milgard Manufacturing Incorporated System for producing pultruded components
US7875675B2 (en) 2005-11-23 2011-01-25 Milgard Manufacturing Incorporated Resin for composite structures
US8519050B2 (en) 2005-11-23 2013-08-27 Milgard Manufacturing Incorporated Resin for composite structures
US20090039551A1 (en) * 2006-03-20 2009-02-12 Henkel Ag & Co. Kgaa Soft crosslinkable polyurethane materials
WO2007107210A1 (en) * 2006-03-20 2007-09-27 Henkel Ag & Co. Kgaa Soft crosslinkable polyurethane materials
US8455679B2 (en) 2008-12-12 2013-06-04 Basf Se Prepolymer systems having reduced monomeric isocyanate contents
US20100152381A1 (en) * 2008-12-12 2010-06-17 Savino Thomas G Prepolymer systems having reduced monomeric isocyanate contents
RU2570199C2 (en) * 2010-03-18 2015-12-10 ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи Method of producing long fibre-reinforced polyurethanes containing granular filler
CN102791757A (en) * 2010-03-18 2012-11-21 陶氏环球技术有限责任公司 Process for making long fiber-reinforced polyurethanes that contain particulate fillers
US9441067B2 (en) 2010-03-18 2016-09-13 Dow Global Technologies Llc Process for making long fiber-reinforced polyurethanes that contain particulate fillers
ITMI20100440A1 (en) * 2010-03-18 2011-09-19 Dow Global Technologies Inc Process for the preparation of polyurethanes reinforced with long fibers that contain particulate fillers
WO2011113768A1 (en) * 2010-03-18 2011-09-22 Dow Global Technologies Llc Process for making long fiber-reinforced polyurethanes that contain particulate fillers
CN102791757B (en) * 2010-03-18 2015-05-27 陶氏环球技术有限责任公司 Process for making long fiber-reinforced polyurethanes that contain particulate fillers
WO2013072380A3 (en) * 2011-11-16 2014-04-03 Soudal Improved polyurethane foam composition
WO2013072380A2 (en) 2011-11-16 2013-05-23 Soudal Improved polyurethane foam composition
US10059794B2 (en) 2011-11-16 2018-08-28 Soudal Polyurethane foam composition
US20160297918A1 (en) * 2013-12-09 2016-10-13 Dow Global Technologies Llc Improved polyurethane prepolymers having little or no plasticizer and their use in vehicular glass adhesives
US9868810B2 (en) * 2013-12-09 2018-01-16 Dow Global Technologies Llc Polyurethane prepolymers having little or no plasticizer and their use in vehicular glass adhesives

Also Published As

Publication number Publication date
AU634480B2 (en) 1993-02-25
EP0422080A1 (en) 1991-04-17
AT126525T (en) 1995-09-15
JPH03505468A (en) 1991-11-28
EP0422080B1 (en) 1995-08-16
BR8907502A (en) 1991-05-28
DE68923879D1 (en) 1995-09-21
AU3843589A (en) 1990-01-12
CA1333437C (en) 1994-12-06
DE68923879T2 (en) 1996-02-08
WO1989012654A1 (en) 1989-12-28
EP0422080A4 (en) 1992-03-11

Similar Documents

Publication Publication Date Title
US3372083A (en) Compositions and articles from the reaction of an isocyanate terminated polyurethaneand the isocyanate adduct of bitumen
US4585803A (en) Internal mold release compositions
US7056976B2 (en) Pultrusion systems and process
US4582887A (en) Reaction injection molded elastomers
EP0546771B1 (en) Two-component urethame adhesive compositions
AU760158B2 (en) Polyisocyanurate compositions and composites
US4607090A (en) Reaction injection molded elastomers
US4246363A (en) Reaction injection molded polyurethanes having particular flexural modulus factors and at least two thermal transition temperatures in a particular range
JP3097854B2 (en) Manufacturing method of polyurethanes
EP0312365B1 (en) Polyisocyanate compositions
CA1141878A (en) Thermosetting molding compositions and a process for the production of moldings
CA1201244A (en) Polyurea-polyurethane acrylate polymer dispersions
CA1172793A (en) Amine modified polyurethane elastomers
US7794817B2 (en) Filled polymer composite and synthetic building material compositions
US4376834A (en) Polyurethane prepared by reaction of an organic polyisocyanate, a chain extender and an isocyanate-reactive material of m.w. 500-20,000 characterized by the use of only 2-25 percent by weight of the latter material
CA1278648C (en) Process for producing polyurethane foams using foam modifiers
US3726827A (en) Rapid-setting non-elastomeric polyurethane compositions
CA1269477A (en) Mixed diamine chain extender
US4385133A (en) Novel compositions and process
US6331577B1 (en) Process for producing elastic polyurethane moldings with compact surfaces and cellular cores
US6043313A (en) Thermoplastic polyurethane additives for improved polymer matrix composites and methods of making and using therefor
US3294713A (en) Organic polysocyanates and polyurethanes prepared therefrom
US6887911B2 (en) Molded foam articles prepared with reduced mold residence time and improved quality
US4383051A (en) Process for the preparation of polyurethane plastics using dianhydro-hexite diols
EP0035389B1 (en) Process for preparing integral skin microcellular polyester base polyurethane elastomers, the elastomers per se isocyanate curable compositions and two component combinations for producing the elastomers and cast shoe soles attached to shoe uppers

Legal Events

Date Code Title Description
AS Assignment

Owner name: DOW CHEMICAL COMPANY, THE, MICHIGAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:NELSON, DONALD L.;WASZECIAK, DOUGLAS P.;REEL/FRAME:005123/0720

Effective date: 19880624

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12